U.S. patent application number 11/258287 was filed with the patent office on 2006-05-04 for multilayered pipes comprising hydrolysis resistant polyamides.
Invention is credited to Robert B. JR. Fish, Marvin M. Martens, Steven A. Mestemacher, Rolando U. Pagilagan.
Application Number | 20060093772 11/258287 |
Document ID | / |
Family ID | 35871221 |
Filed Date | 2006-05-04 |
United States Patent
Application |
20060093772 |
Kind Code |
A1 |
Fish; Robert B. JR. ; et
al. |
May 4, 2006 |
Multilayered pipes comprising hydrolysis resistant polyamides
Abstract
Multilayered pipes are provided wherein at least one layer
comprises polyamide compositions having good hydrolysis resistance
and that may optionally contain plasticizer. Such pipes are suited
for applications transporting hydrocarbons. The pipes of the
present invention may be in the form of flexible pipes.
Inventors: |
Fish; Robert B. JR.;
(Parkersburg, WV) ; Martens; Marvin M.; (Vienna,
WV) ; Mestemacher; Steven A.; (Parkersburg, WV)
; Pagilagan; Rolando U.; (Parkersburg, WV) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY;LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1128
4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Family ID: |
35871221 |
Appl. No.: |
11/258287 |
Filed: |
October 25, 2005 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
60622497 |
Oct 27, 2004 |
|
|
|
Current U.S.
Class: |
428/36.91 |
Current CPC
Class: |
C08L 77/00 20130101;
B32B 2307/714 20130101; Y10T 428/1393 20150115; B32B 2250/02
20130101; F16L 11/04 20130101; F16L 9/133 20130101; B32B 1/08
20130101; C08L 77/00 20130101; B32B 2597/00 20130101; C08L 77/06
20130101; B32B 2264/12 20130101; C08L 2666/20 20130101; B32B 27/08
20130101; C08L 2666/20 20130101; B32B 27/22 20130101; F16L 11/08
20130101; B32B 27/18 20130101; B32B 15/088 20130101; C08L 77/06
20130101; B32B 27/34 20130101; F16L 9/12 20130101 |
Class at
Publication: |
428/036.91 |
International
Class: |
B32B 1/08 20060101
B32B001/08 |
Claims
1. A multi-layered pipe comprising at least two concentric layers,
wherein at least one layer comprises a polyamide composition
comprising a polyamide comprising: (a) about 2 to about 35 mole
percent of repeat units derived from at least one aromatic
dicarboxylic acid having 4 to 16 carbon atoms and/or at least one
alicyclic dicarboxylic acid having 8 to 20 carbon atoms and at
least one aliphatic diamine having 4 to 20 carbon atoms and/or at
least one alicyclic diamine having 6 to 20 carbon atoms; and (b)
about 65 to about 98 mole percent of repeat units derived from at
least one aliphatic dicarboxylic acid having 6 to 36 carbon atoms
and at least one aliphatic diamine having 4 to 20 carbon atoms
and/or at least one alicyclic diamine having 6 to 20 carbon atoms,
and/or repeat units derived from at least one lactam having 4 to 20
carbon atoms and/or aminocarboxylic acid having 4 to 20 carbon
atoms.
2. The pipe of claim 1, wherein repeat units (a) are derived from
terephthalic acid and hexamethylenediamine.
3. The pipe of claim 1, wherein repeat units (a) are derived from
isophthalic acid and hexamethylenediamine.
4. The pipe of claim 1, wherein repeat units (b) are derived from
decanedioic acid and hexamethylenediamine.
5. The pipe of claim 1, wherein repeat units (b) are derived from
dodecanedioic acid and hexamethylenediamine.
6. The pipe of claim 2, wherein repeat units (b) are derived from
decanedioic acid and hexamethylenediamine.
7. The pipe of claim 2, wherein repeat units (b) are derived from
dodecanedioic acid and hexamethylenediamine
8. The pipe of claim 1, wherein the polyamide composition further
comprises about 1 to about 20 weight percent, based on the total
weight of the composition, of a plasticizer.
9. The pipe of claim 8, wherein the plasticizer is a
sulfonamide.
10. The pipe of claim 8, wherein the plasticizer is one or more of
N-butylbenzenesulfonamide, N-(2-hydroxypropyl)benzenesulfonamide,
N-ethyl-o-toluenesulfonamide, N-ethyl-p-toluenesulfonamide,
o-toluenesulfonamide, and p-toluenesulfonamide.
11. The pipe of claim 1, wherein the polyamide composition further
comprises one or more of thermal oxidative, and/or light
stabilizers; mold release agents; colorants; and lubricants.
12. The pipe of claim 1 in the form of a flexible pipe.
13. The pipe of claim 12, wherein the pipe is an undersea oil pipe.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 60/622,497, filed Oct. 27, 2004.
FIELD OF THE INVENTION
[0002] The present invention relates multilayered pipes comprising
hydrolysis resistant polyamide compositions that may optionally
comprise plasticizer. The pipes may be in the form of flexible
pipes.
BACKGROUND OF THE INVENTION
[0003] Pipes are used to convey a wide variety of liquids, gases,
and fine solids under a wide variety of conditions. Pipes are
typically made from metals, polymers, and metal-polymer composite
structures, depending on the materials to be conveyed and the
conditions the pipes will be subjected to during use. Because they
have good chemical resistance, good physical properties, and can be
conveniently formed into pipes with a variety of diameters and
incorporated into multilayered pipes, polyamides are often a
desirable material to use for pipes. Multilayered pipes have many
applications, particularly in the oil and gas industry, where they
are used to transport oil and gas from undersea and under-land
wells to the surface, across the surface both above and below
ground to refineries, to and from storage tanks, etc. However, many
applications using multi-layered pipes require elevated
temperatures. Examples include an undersea oil pipe that comes into
contact with hot oil from the earth's interior. Under such
conditions, the amide bonds of many polyamides may be susceptible
to hydrolysis in the presence of water and the rate of hydrolysis
increases with temperature. Hydrolysis of the amide bonds can cause
a reduction in molecular weight and concomitant loss in physical
properties that can result in failure of the pipe during use. Such
a failure can be catastrophic, with the loss of fluid causing
undesirable consequences ranging from the impairment of the
performance of the device within which the piping is incorporated,
to contact of the fluid with the surrounding environment.
[0004] Aliphatic polyamides such as polyamide 6,12 or polyamide 11
are frequently used to make multilayered pipes, but many
applications require greater hydrolysis resistance than can be
obtained from currently available polyamides.
[0005] It would be desirable to obtain a pipe comprising polyamide
that has both improved hydrolysis resistance and can be
conveniently plasticized to give it the flexibility needed to be
useful in many applications. A further object of the present
invention is to provide piping, tubing and the like which is
readily prepared by conventional means well accepted in the field.
A feature of the present invention is that the instant compositions
are formable into any of a wide variety of structural designs and
configurations. An advantage of the present invention is that these
structural components can be further optimized for specialized
functions with the addition of an assortment of additives including
stabilizers, colorants, molding agents, and the like. These and
other objects, features and advantages of the invention will become
better understood upon having reference to the following
description of the invention.
SUMMARY OF THE INVENTION
[0006] There is disclosed and claimed herein multi-layered pipes
comprising at least two concentric layers, wherein at least one
layer comprises a polyamide composition comprising a polyamide
comprising: [0007] (a) about 2 to about 35 mole percent of repeat
units derived from at least one aromatic dicarboxylic acid having 4
to 16 carbon atoms and/or at least one alicyclic dicarboxylic acid
having 8 to 20 carbon atoms and at least one aliphatic diamine
having 4 to 20 carbon atoms and/or at least one alicyclic diamine
having 6 to 20 carbon atoms; and [0008] (b) about 65 to about 98
mole percent of repeat units derived from at least one aliphatic
dicarboxylic acid having 6 to 36 carbon atoms and at least one
aliphatic diamine having 4 to 20 carbon atoms and/or at least one
alicyclic diamine having 6 to 20 carbon atoms, and/or repeat units
derived from at least one lactam having 4 to 20 carbon atoms and/or
aminocarboxylic acid having 4 to 20 carbon atoms. The polyamide
composition may optionally further comprise plasticizer.
DETAILED DESCRIPTION OF THE INVENTION
[0009] There are a number of terms used throughout the
specification for which the following will be of assistance in
understanding their scope and meaning. As used herein and as will
be understood by those skilled in the art, the terms "terephthalic
acid", "isophthalic acid", and "dicarboxylic acid/dioic acid" refer
also to the corresponding carboxylic acid derivatives of these
materials, which can include carboxylic acid esters, diesters, and
acid chlorides. Moreover and as used herein, and as will be
understood by one skilled in the art, the term "hydrolysis
resistant" in conjunction with a polyamide refers to the ability of
the polyamide to retain its molecular weight upon exposure to
water.
[0010] As used herein, the term "multilayered pipes" refers to
structures defining a cavity therethrough for conducting a fluid,
including without limitation any liquid, gas, or finely divided
solid. They may have a circular or roughly circular (e.g. oval)
cross-section. However more generally the pipes may be shaped into
seemingly limitless geometries so long as they define a passageway
therethrough. For example suitable shapes may include polygonal
shapes and may even incorporate more that one shape along the
length thereof. The pipes may further be joined together by
suitable means to form T-sections, branches, and the like. The
multilayered pipes may be flexible or stiff and have a variety of
wall thicknesses and (in the event that the pipes are circular in
cross section) diameters. The pipes comprise at least two layers,
wherein at least one layer comprises a polyamide composition. The
layers are concentric and at least two of the layers are made from
different materials. Other layers may comprise other polymeric
materials or metals. Polymeric materials include thermoplastic
polymers and thermoset polymers such as an epoxy resin. Other
layers may be formed from a tape or other wrapping material, which
made comprise a polyamide composition, other polymer material,
metal, or other material. Other layers may also comprise a
polymeric and/or metal mesh or sleeve.
[0011] The multilayered pipes of the present invention are
particularly suitable for use in transporting hydrocarbons,
including crude oil, natural gas, and petrochemicals. The
hydrocarbons may contain water and/or alcohols.
[0012] The multilayered pipes of the present invention comprise at
least one layer comprising a polyamide composition. The polyamide
composition comprises a polyamide comprising about 2 to about 35
mole percent, or preferably about 4 to about 20 mole percent, or
more preferably about 5 to about 11 mole percent of repeat units
(a) derived from at least one aromatic dicarboxylic acid having 4
to 16 carbon atoms and/or at least one alicyclic dicarboxylic acid
having 8 to 20 carbon atoms and at least one aliphatic diamine
having 4 to 20 carbon atoms and/or at least one alicyclic diamine
having 6 to 20 carbon atoms. The polyamide comprises about 65 to
about 98 mole percent, or preferably about 80 to about 96 mole
percent, or more preferably about 89 to about 95 mole percent of
repeat units (b) derived from at least one aliphatic diamine having
4 to 20 carbon atoms and/or at least one alicyclic diamine having 6
to 20 carbon atoms and at least one aliphatic dicarboxylic acid
having 6 to 36 carbon atoms and/or repeat units derived from at
least one lactam and/or aminocarboxylic acid having 4 to 20 carbon
atoms.
[0013] By "aromatic dicarboxylic acid" is meant dicarboxylic acids
in which each carboxyl group is directly bonded to an aromatic
ring. Examples of suitable aromatic dicarboxylic acids include
terephthalic acid; isophthalic acid; 1,5-nathphalenedicarboxylic
acid; 2,6-nathphalenedicarboxylic acid; and
2,7-nathphalenedicarboxylic acid. Terephthalic acid and isophthalic
acid are preferred. By "alicyclic dicarboxylic acid" is meant
dicarboxylic acids in which each carboxyl group is directly bonded
to a saturated hydrocarbon ring. An example of a suitable alicyclic
dicarboxylic acids includes 1,4-cyclohexanedicarboylic acid. By
"alicyclic diamine" is meant diamines possessing two primary or
secondary amine groups and containing at least one saturated
hydrocarbon ring. Alicyclic diamines preferably contain at least
one cyclohexane moiety. Examples of suitable alicyclic diamines
include 1-amino-3-aminomethyl-3,5,5,trimethylcyclohexane;
1,4-bis(aminomethyl)cyclohexane; and bis(p-aminocyclohexyl)methane.
Any stereoisomers of the alicyclic diamines may be used.
[0014] Examples of aliphatic dicarboxylic acids having 6 to 36
carbon atoms include adipic acid, nonanedioic acid, decanedioic
acid (also known as sebacic acid), undecanedioic acid,
dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid.
The aliphatic diamines having 4 to 20 carbon atoms may be linear or
branched. Examples of preferred diamines include
hexamethylenediamine, 2-methylpentamethylenediamine;
1,8-diaminooctane; methyl-1,8-diaminooctane; 1,9-diaminononane;
1,10-diaminodecane; and 1,12-diaminedodecane. Examples of lactams
include caprolactam and laurolactam. An example of an
aminocarboxylic acid includes aminodecanoic acid.
[0015] Preferred polyamides are semiaromatic polyamides. The
polyamides preferably comprise repeat units (a) that are derived
from terephthalic acid and/or isophthalic acid and
hexamethylenediamine and repeats units (b) that are derived from at
least one of nonanedioic acid and hexamethylenediamine; decanedioic
acid and hexamethylenediamine; undecanedioic acid and
hexamethylenediamine; dodecanedioic acid and hexamethylenediamine;
tridecanedioic acid and hexamethylenediamine; tetradecanedioic acid
and hexamethylenediamine; caprolactam; laurolactam; and
11-aminoundecanoic acid.
[0016] A preferred polyamide comprises from about 3 to about 40
mole percent of repeat units derived from terephthalic acid and
hexamethylenediamine and complementally from about 60 to about 97
mole percent of repeat units derived from dodecanedioic acid and
hexamethylenediamine. Another preferred polyamide comprises from
about 3 to about 40 mole percent of repeat units derived
terephthalic acid and hexamethylenediamine and complementally from
about 60 to about 97 mole percent of repeat units derived from
decanedioic acid and hexamethylenediamine.
[0017] The polyamide used in the present invention may be prepared
by any means known to those skilled in the art, such as in a batch
process using, for example, an autoclave or using a continuous
process. See, for example, Kohan, M. I. Ed. Nylon Plastics
Handbook, Hanser: Munich, 1995; pp. 13-32. Additives such as
lubricants, antifoaming agents, and end-capping agents may be added
to the polymerization mixture.
[0018] The polyamide composition used in the present invention may
optionally comprise additives. A preferred additive is at least one
plasticizer. The plasticizer will preferably be miscible with the
polyamide. Examples of suitable plasticizers include sulfonamides,
preferably aromatic sulfonamides such as benzenesulfonamides and
toluenesulfonamides. Examples of suitable sulfonamides include
N-alkyl benzenesulfonamides and toluenesufonamides, such as
N-butylbenzenesulfonamide, N-(2-hydroxypropyl)benzenesulfonamide,
N-ethyl-o-toluenesulfonamide, N-ethyl-p-toluenesulfonamide,
o-toluenesulfonamide, p-toluenesulfonamide, and the like. Preferred
are N-butylbenzenesulfonamide, N-ethyl-o-toluenesulfonamide, and
N-ethyl-p-toluenesulfonamide.
[0019] The plasticizer may be incorporated into the composition by
melt-blending the polymer with plasticizer and, optionally, other
ingredients, or during polymerization. If the plasticizer is
incorporated during polymerization, the polyamide monomers are
blended with one or more plasticizers prior to starting the
polymerization cycle and the blend is introduced to the
polymerization reactor. Alternatively, the plasticizer can be added
to the reactor during the polymerization cycle.
[0020] When used, the plasticizer will be present in the
composition in about 1 to about 20 weight percent, or more
preferably in about 6 to about 18 weight percent, or yet more
preferably in about 8 to about 15 weight percent, wherein the
weight percentages are based on the total weight of the
composition.
[0021] The polyamide composition used in the present invention may
optionally comprise additional additives such as impact modifiers;
thermal, oxidative, and/or light stabilizers; colorants;
lubricants; mold release agents; and the like. Such additives can
be added in conventional amounts according to the desired
properties of the resulting material, and the control of these
amounts versus the desired properties is within the knowledge of
the skilled artisan.
[0022] When present, additives may be incorporated into the
polyamide composition used in the present invention by
melt-blending using any known methods. The component materials may
be mixed to homogeneity using a melt-mixer such as a single or
twin-screw extruder, blender, kneader, Banbury mixer, etc. to give
a polyamide composition. Or, part of the materials may be mixed in
a melt-mixer, and the rest of the materials may then be added and
further melt-mixed until homogeneous.
[0023] The pipes of the present invention may be formed by any
method known to those skilled in the art, such as extrusion. The
polyamide composition used in the present invention may be extruded
over one or more additional layers, including polymeric and metal
layers. Additional layers may be added to a pipe comprising at
least one layer comprising the polyamide used in the present
invention by wrapping one or more additional layers around a pipe
comprising at least one layer comprising the polyamide used in the
present invention. A polymeric layer made form an additional
polymeric material may be added to a pipe comprising at least one
layer comprising the polyamide used in the present invention by
extrusion. The pipes will preferably have sufficient flexibility to
allow them to be conveniently stored and transported.
[0024] In one embodiment, the multilayered pipes of the present
invention are flexible pipes used in crude oil production to
transport oil from wells. Particularly preferred are undersea
flexible pipes used to transport crude oil from undersea wells to
the surface. Flexible pipes are often subjected to internal
pressure and external stressing. Such pipes are described in U.S.
Pat. No. 6,053,213, which is hereby incorporated herein by
reference. Such pipes are also described in API 17B and 17J,
published by the American Petroleum Institute under the title
"Recommended Practice for Flexible Pipe." Flexible pipe is
preferably assembled as a composite structure comprising metal and
polymer layers where the structure allows large deflections without
a significant increase in bending stresses. At least one layer of
the flexible pipe comprises the polyamide composition used in the
present invention.
[0025] The flexible pipe may be of an unbonded type where the
layers may move to a certain degree relative to one another. The
layers of a flexible pipe may include a carcass that prevents the
pipe from being crushed under outside pressure, which may comprise
a fabric tape; an internal sheath comprising a polymer; a pressure
vault; one or more armor layers; an anti-collapse sheath; and/or an
outer sheath comprising polymer. Not all of these layers need be
present and additional layers, such a metal tube that may be
corrugated, may also be present. Anti-wear strips may be present
between metal layers and may be in the form of a tape wrapped
around metal layer beneath it. The anti-wear strips will preferably
comprise the polyamide composition used in the present invention.
The pressure vault may comprise shaped interlocked metal wires. At
least one of the sheath layers may comprise the polyamide
composition used in the present invention.
EXAMPLES
Determination of Hydrolysis Resistance
[0026] It is well known in the art that when hydrolyzed, polyamides
often lose physical properties. The loss of physical properties is
often directly correlated with a decrease in inherent viscosity of
the polyamide. The degree of degradation may be conveniently
studied by observing the decrease of a polyamide's inherent
viscosity over time. Such a method is described in API (American
Petroleum Institute) Technical Report 17TR2, June 2003, and is the
method upon which the following procedure is based.
[0027] Hydrolysis resistance testing was done on compositions
molded into standard ISO tensile bars that were immersed in
distilled water in a pressure vessel. The water and samples were
held under vacuum for 30 minutes and then high-purity argon was
bubbled through the water for 30 minutes to remove dissolved
oxygen. The vessel was then sealed and placed in a conventional
electrical heating mantle. The temperature in the vessel was
controlled by use of a thermocouple in a thermowell in the wall of
the vessel and was maintained at 105.+-.1.degree. C. and samples
were withdrawn at intervals and their inherent viscosities and
plasticizer contents were measured. After each sample was
withdrawn, the water was replaced, a new sample was added, and the
procedure repeated.
[0028] Inherent viscosity (IV) was measured by dissolving a sample
of the polymer in m-cresol and measuring the IV in a capillary
viscometer following ASTM 2857. Because plasticizer present in the
samples could leach out during the hydrolysis testing and hence
affect the measured IV, it was necessary to correct for the amount
of plasticizer present in each sample.
[0029] In order to correct for the amount of plasticizer in each
sample, the weight percent plasticizer content was measured by
heating samples under vacuum and measuring the weight loss that
occurred during heating. The inherent viscosity corrected for
plasticizer content (CIV) was calculated by formula (1) (where
plasticizer % is the weight percentage plasticizer present in the
sample): CIV = IV ( 100 .times. % - plasticizer .times. .times. % )
* 100 .times. % ( 1 ) ##EQU1## The percent loss of CIV was
calculated by formula (2): % .times. .times. CIV .times. .times.
loss = CIV .function. ( t = x ) CIV .function. ( t = 0 ) * 100
.times. % ( 2 ) ##EQU2## where CIV.sub.(t=x) is the CIV for the
sample taken at time x and CIV.sub.(t=0) is the CIV for a sample
taken before hydrolysis testing.
[0030] The % CIV loss was plotted as a function of
log.sub.10(time), where time is the amount of time in hours each
sample was exposed to water in the pressure vessel at
105.+-.1.degree. C. A linear least squares fit was made to the plot
of % CIV loss as a function of log.sub.10(time) and a value for %
CIV loss at 500 hours was calculated by interpolation from the
least squares fit. The results are reported below.
COMPARATIVE EXAMPLE 1
[0031] A polyamide 6,12 salt solution having a pH of about 8.0 and
was prepared by dissolving hexamethylenediamine and
1,12-dodecanedioic acid in water. The concentration of salt in the
solution was 45 percent by weight. The salt solution (5,700 lbs)
was charged to a vessel. A conventional antifoaming agent (250 g of
a 10 percent by weight aqueous solution), phosphoric acid (about
0.18 lbs of a 78 percent weight aqueous solution), and
N-butylbenzenesulfonamide (490 lbs) were added to the vessel. The
resulting solution was then concentrated to 80 weight percent while
heating under pressure. The solution was then charged to an
autoclave and heated. The pressure was allowed to rise to 265 psia.
Heating was continued until the temperature of the reaction reached
255.degree. C., during which time steam was vented to maintain the
pressure at 265 psia The pressure was then reduced slowly to 14.7
psia while the reaction temperature was allowed to rise to
280.degree. C. The pressure was held at 14.7 psia and the
temperature at 280.degree. C. for 30 minutes. The resulting polymer
melt was extruded into strands, cooled, and cut into pellets that
were dried at 160.degree. C. under nitrogen. The resulting polymer
is referred to hereafter as "C1."
[0032] C1 (98.4 weight percent) was dry blended by tumbling in a
drum with the stabilizers Tinuvin.RTM. 234 (0.5 weight percent),
Irgafos.RTM. 168 (0.4 weight percent); Irganox.RTM. 1098 (0.4
weight percent); Chimassorb.RTM. 944F (0.3 weight percent). Each
stabilizer is available from Ciba Specialty Chemicals, Tarrytown,
N.Y. The resulting blend was then molded into standard ISO tensile
bars. The bars were subjected to hydrolysis testing as described
above and the results are shown in Table 1. The % CIV loss at 500
hours was calculated to be 39.8% using the method described above.
TABLE-US-00001 TABLE 1 Exposure Plasticizer Measured CIV loss
Sample time (h) content (wt. %) IV CIV (%) 1 0 10.3 1.55 1.73 0 2
20 7.6 1.548 1.68 3.0 3 76 6.7 1.472 1.58 8.9 4 238 3.6 1.158 1.20
30.5 5 832 1.4 0.931 0.94 45.4 6 1153 0.8 0.878 0.89 48.8 7 1153
0.8 0.877 0.88 48.8
EXAMPLE 1
[0033] A polyamide 6,12 salt solution having a pH of about 7.7 was
prepared by dissolving hexamethylenediamine and 1,12-dodecanedioic
acid in water. The solution had a concentration of about 44.6
weight percent. A polyamide 6,T salt solution having a pH of about
8 was prepared by dissolving hexamethylenediamine and terephthalic
acid in water. The 6,T salt solution had a concentration of about
40 weight percent. Both solutions were charged into an autoclave. A
conventional antifoaming agent (10 g of a 10 percent by weight
aqueous solution), sodium hypophosphite (0.014 g), and
N-butylbenzenesulfonamide (51.1 g) were added to the autoclave. The
resulting solution was then concentrated to 80 weight percent while
heating under pressure. The concentrated solution was then heated
and the pressure allowed to rise to 240 psia. Heating was continued
until the temperature of the reaction reached 241.degree. C.,
during which time steam was vented to maintain the pressure at 240
psia. The pressure was then slowly reduced to 14.7 psia while the
reaction temperature was allowed to rise to 270.degree. C. The
pressure was held at 14.7 psia and the temperature at 280.degree.
C. for 60 minutes. The resulting polymer melt was extruded into a
strand, cooled, and cut into pellets. The resulting polymer is
referred to hereafter as "E1."
[0034] E1 (98.4 weight percent) was dry blended by tumbling in a
drum with the stabilizers Tinuvin.RTM. 234 (0.5 weight percent),
Irgafos.RTM. 168 (0.4 weight percent); Irganox.RTM. 1098 (0.4
weight percent); Chimassorb.RTM. 944F (0.3 weight percent). Each
stabilizer is available from Ciba Specialty Chemicals, Tarrytown,
N.Y. The resulting blend was then molded into standard ISO tensile
bars. The bars were subjected to hydrolysis testing as described
above and the results are shown in Table 2. The % CIV loss at 500
hours was calculated to be 29.8% using the method described above.
TABLE-US-00002 TABLE 2 Exposure Plasticizer Measured CIV loss
Sample time (h) content (wt. %) IV CIV (%) 1 0 5.9 1.056 1.12 0 2
18 3.1 0.973 1.00 10.5 3 127 1.6 0.822 0.84 25.6 4 361.5 1.3 0.787
0.80 28.9 5 839 0.3 0.781 0.78 30.2
[0035] A comparison of the results of Example 1, wherein the
composition comprises a polyamide comprising repeat units derived
from hexamethylenediamine and terephthalic acid and
hexamethylenediamine and 1,12-dodecanedioic acid, with those of
Comparative Example 1, wherein the composition comprises a
polyamide comprising only repeat units derived from
hexamethylenediamine and 1,12-dodecanedioic acid, demonstrates that
incorporation of repeat units derived from hexamethylenediamine and
terephthalic acid leads to a substantial decrease in % CIV loss,
and hence improvement in hydrolysis resistance.
* * * * *